Synthesis,structure, reactivity and electrochemistry of a new molybdenum(0) dithiocarbamato complex, [Et4N][Mo(CO)4(S2CNEt2)] |
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| Institution: | 1. State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;2. Shenzhen Institute of Huazhong, University of Science & Technology, Shenzhen, Guangdong 518000, China;1. Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería, 8, 33006, Oviedo, Spain;2. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, G1 1XL, Glasgow, UK;3. GIR MIOMeT-IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, C/ Paseo de Belén 7, 47011, Valladolid, Spain;4. Centro de Investigación en Nanomateriales y Nanotecnología (CINN), CSIC-Universidad de Oviedo-Principado de Asturias, Avenida de la Vega 4-6, 33940, El Entrego, Spain |
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| Abstract: | A new molybdenum(0) dithiocarbamato complex Et4N] Mo(CO)4(S2CNEt2)] (1) has been synthesized by the reaction of Mo(CO)6, NaS2CNEt2 and Et4NCl in MeCN and characterized by routine elemental analysis, spectroscopy methods. The crystal and molecular structure of 1 was determined from X-ray three dimension data. 1 crystallizes in the orthorhombic, space group Pbc21 with a= 8.148(2), b=19.618(2), c=14.354(2) Å; V=2294 Å3; Z=4; R1=0.052, R2=0.058 for 1308 independent reflections with I ? 3σ(I). The geometry around Mo(0) atom in the anion Mo(CO)4(S2CNEt2)]- of 1 is distorted octahedral with a small SMoS of 67.70° and a small angle of 3.6° between plane MoSS and MoC(1)C(2). Two groups of MoCO bond distances and the longer MoS bond distance observed in 1 are similar to that in the dinuclear Mo(0) complexes containing SR bridges but very different from those observed in the dithiocarbamato complexes of Mo in higher oxidation states. Different oxidizing products containing Mo in II-V oxidation states Mo(CO)2(S2CNEt2)2, MoO(S2CNEt2)2, Mo2O3(S2CNEt2)4 and Mo2O4(S2CNEt2)2 were isolated from the oxidation of 1 with I2 (or in the presence of traces of air). The electrochemical behavior of 1 in MeCN was investigated by cyclic voltammetry at Pt and C electrodes. The anodic peaks observed at 0.04, 0.14, 0.26 and 0.44 V versus SCE implied that 1 probably underwent oxidation in company with dissociation of dithiocarbamate and substitution of carbonyls resulting in several complexes of Mo in different oxidation states. The relationship between reactivity and structure is also discussed. |
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